CN1784267A - A reactor system and process for the manufacture of ethylene oxide - Google Patents
A reactor system and process for the manufacture of ethylene oxide Download PDFInfo
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- CN1784267A CN1784267A CNA2004800122319A CN200480012231A CN1784267A CN 1784267 A CN1784267 A CN 1784267A CN A2004800122319 A CNA2004800122319 A CN A2004800122319A CN 200480012231 A CN200480012231 A CN 200480012231A CN 1784267 A CN1784267 A CN 1784267A
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 230000008569 process Effects 0.000 title description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 83
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000005977 Ethylene Substances 0.000 claims abstract description 9
- 239000012876 carrier material Substances 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 238000007493 shaping process Methods 0.000 claims description 25
- 229910052709 silver Inorganic materials 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 230000008676 import Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 3
- 230000001131 transforming effect Effects 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 description 18
- 239000000969 carrier Substances 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000006872 improvement Effects 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 229940117927 ethylene oxide Drugs 0.000 description 6
- 229910052702 rhenium Inorganic materials 0.000 description 6
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000013529 heat transfer fluid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007634 remodeling Methods 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001915 proofreading effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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- B01J35/50—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/30—Loose or shaped packing elements, e.g. Raschig rings or Berl saddles, for pouring into the apparatus for mass or heat transfer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
- B01J8/067—Heating or cooling the reactor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/30—Details relating to random packing elements
- B01J2219/302—Basic shape of the elements
- B01J2219/30223—Cylinder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/30—Details relating to random packing elements
- B01J2219/304—Composition or microstructure of the elements
- B01J2219/30416—Ceramic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/30—Details relating to random packing elements
- B01J2219/304—Composition or microstructure of the elements
- B01J2219/30475—Composition or microstructure of the elements comprising catalytically active material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/30—Details relating to random packing elements
- B01J2219/31—Size details
- B01J2219/312—Sizes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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- Chemical Kinetics & Catalysis (AREA)
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- Thermal Sciences (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
Abstract
A reactor system for the oxidation of ethylene to ethylene oxide. The reactor system includes a reactor tube that contains a packed bed of shaped support material that can include a catalytic component. The shaped support material has a hollow cylinder geometric configuration. The reactor system has specific combinations of reactor tube and catalyst system geometries.
Description
Technical field
The present invention relates to reactor assembly.Another aspect of the present invention relates to reactor assembly and is used to make oxirane.
Prior art
Oxirane is a kind of important industrial chemical, and it supplies manufacturing chemistry product such as ethylene glycol, glycol ether, alkanolamine and detergent as charging.A method of making oxirane is the catalytic partial oxidation of ethene and oxygen.In the method, contain the incoming flow of ethene and oxygen by being contained on the catalyst bed in the reaction zone that remains on special reaction condition.Usually, Ethylene Oxidation Reactor is to have to fill the supported catalyst particle is contained in the packed bed in the reactor tube with formation a plurality of parallel elongate form of tubes.Carrier can be Any shape, for example, and spherical, ball shape, ring-type and sheet.Special support shapes of wishing is a hollow cylindrical.
A problem of using the packed bed of hollow cylinder supported catalyst particle to be suffered in the ethylene oxidation reactions district is to be difficult in to cross the appropriate balance that has between pressure drop that catalyst bed takes place and catalyst bed packed density in the operation of ethylene oxide treatment.Catalyst performance is improved along with the catalyst packed density of the increase in the ethylene oxidation reactions pipe usually; Yet, cross reactor not the increase of desired pressure drop follow the catalyst packed density of increase usually.
When hope was made oxirane by the selective oxidation of ethene, utilization had the catalyst filling bed of high packed density but crosses the reactor assembly that the catalyst filling bed accessory has minimum pressure drop.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of reactor assembly that is applicable to the catalytic partial oxidation of oxirane, it has high packed density but the catalyst filling bed of suitable pressure drop still was provided in its operating period.
In view of the content of following explanation, can make other aspects of the present invention, purpose and a plurality of advantage more clear.
In one aspect, the invention provides a kind of reactor assembly, comprising:
One has the pipe range in defined reaction district and the elongated tubular of caliber; The packed bed of carrier material of wherein being shaped is included in this reaction zone; And the carrier material that wherein is shaped has the hollow cylinder geometry that is limited by nominal length, nominal outside diameter and nominal bore diameter, makes that nominal length is 0.5 to 2 to the ratio ranges of nominal outside diameter, and makes
When caliber during less than 28 millimeters, the ratio of nominal outside diameter and nominal bore diameter surpasses 2.3, and the ratio ranges of caliber and external diameter is 1.5 to 7, reaches
When caliber was at least 28 millimeters, the ratio of nominal outside diameter and nominal bore diameter surpassed 2.7, and the ratio ranges of caliber and external diameter is 2 to 10.
On the other hand, the invention provides a kind of reactor assembly, comprising:
Have the pipe range in defined reaction district and the elongated tubular of caliber; The packed bed of carrier material of wherein being shaped is included in the reaction zone; And the carrier material that wherein is shaped has the hollow cylinder geometry that is limited by nominal length, nominal outside diameter and nominal bore diameter, makes
The ratio ranges of nominal length and nominal outside diameter is 0.5 to 2, and
The ratio of nominal length and nominal bore diameter provides positive result of the test, as the qualification of following institute, and feasible
When caliber during less than 28 millimeters, the ratio ranges of caliber and nominal outside diameter is 1.5 to 7, and when caliber was at least 28 millimeters, this ratio ranges was 2 to 10.
Here, " positive result of the test " is defined as the quotient reduction of numerical value and the numerical value of packed density of the pressure drop of every unit packed bed length, these numerical value are by being under the 1.136Mpa (150psig) at pressure, the test packed bed obtains in the turbulent flow of nitrogen, relative comparison quotient obtains in an identical manner, except the hollow cylinder geometry of same vehicle material at caliber during less than 28 millimeters, being defined as nominal outside diameter and being 6 millimeters and nominal bore diameter is 2.6 millimeters, and when caliber is at least 28 millimeters, being defined as nominal outside diameter and being 8 millimeters and nominal bore diameter is 3.2 millimeters, and the ratio of nominal length and nominal outside diameter is defined as beyond 1.
According to a further aspect in the invention, a kind of method of making oxirane is provided, comprise that the charging that will comprise ethene and oxygen imports according in the reactor assembly of the present invention, and if any, the autoreactor system recoveries comprises the product of oxirane and unconverted ethene, wherein have the supported catalyst of being carried on system in the reaction zone, it comprises the catalyst component that is carried on the shaping carrier material with hollow cylinder geometry.
In addition, the invention provides a kind of use oxirane for making ethylene glycol, glycol ether or 1, the method for 2-alkanolamine comprises that transforming oxirane becomes ethylene glycol, glycol ether or 1, the 2-alkanolamine, wherein oxirane obtains by the method for preparation according to oxirane of the present invention.
As used herein, in the context of hollow cylinder geometry, term " internal diameter " reaches " aperture " and has same meaning and being used interchangeably in this article.Again, as used herein, term " supporting body " has same meaning with " carrier " and is used interchangeably in this article.
Description of drawings
Fig. 1 illustrates some aspect of reactor assembly of the present invention, and reactor assembly comprises a pipe, and one section packed bed with the shaping carrier material that contains antigravity system of this pipe is filled;
Fig. 2 illustrates the shaping carrier material of antigravity system of the present invention, but this antigravity system has the physical size of hollow cylinder geometry and characterization shaping carrier material;
Fig. 3 is the schematic diagram that comprises the oxirane manufacture method of the specific novel aspect of the present invention;
Fig. 4 represents to be included in pressure drop (" %DP ") and pipe packed density (" %TPD " owing to use the hollow cylinder carrier material of the various sizes (external diameter) with different length and natural scale (" L/D ") to be used in the interior result with respect to 8 millimeters hollow cylinder carrier materials of use standard of 39 mm dia reactor tubes; " %TPD
*" the expression repeating data) data of change (" C (%) ") of aspect;
Fig. 5 represents owing to use that to have nominal length and natural scale be 1.0 and different aperture (" hole ", indicate with millimeter) the hollow cylinder carrier material of various sizes (external diameter) be used in the 39 mm dia reactor tubes with respect to the result of 8 millimeters hollow cylinder carrier materials of use standard, be included in pressure drop (" %DP ") and pipe packed density (" %TPD "; " %TPD* " represents repeating data) data of the change (" C (%) ") of aspect;
Fig. 6 represents to be included in the data of the change (" C (%) ") of pressure drop (" %DP ") and pipe packed density (" %TPD ") aspect owing to use and to have different length the hollow cylinder carrier material of the various sizes (external diameter) of natural scale (" L/D ") is used in the 21 mm dia reactor tubes with respect to the result of 6 millimeters hollow cylinder carrier materials of use standard; And
Fig. 7 be explanation (a) shaping carrier material be the ideal cylinder shape the neighboring the cross section and (b) the shaping carrier material be the accompanying drawing in the cross section, neighboring of departing from the ideal cylinder shape.
The specific embodiment
A kind of method of making oxirane is the catalytic partial oxidation of ethene and oxygen.This method generally is described in " encyclopedia of chemical technology " that Kirk-Othmer compiles, the 9th volume, 432 to 471 pages, John Wiley, London/New York 1980.Tradition Ethylene Oxidation Reactor system is applicable to the present invention, and these systems comprise a plurality of parallel elongate pipes, and it is that 20 millimeters to 60 millimeters and length range are 3 meters to 15 meters that elongated tubular has inside diameter ranges.Also availablely be used in the Ethylene Oxidation Reactor system than bassoon.Pipe is applicable to shell and tube type heat exchanger usually and forms the shell that heat exchanger is put in a branch of confession.Pipe is filled any suitable ethylene oxide catalyst, and it is provided for ethene and becomes oxirane with the selective oxidation of oxygen.The shell side of heat exchanger provides the passage of heat transfer medium to be used to remove the reaction heat that causes owing to the hexene oxidation and is used to be controlled at the interior reaction temperature of pipe that contains ethylene oxide catalyst.
The incoming flow that comprises ethene and oxygen imports in the pipe of reactor assembly, and wherein incoming flow is that 50 ℃ to 400 ℃ and pressure limit are to contact with ethylene oxide catalyst under the 0.15Mpa to 3Mpa in temperature range usually.
Used antigravity system is an antigravity system on the carrier in the above-mentioned typical oxirane autofrettage, and it comprises supporting body or carrier material, catalyst component and also have one or more catalyst promoting agent compositions to deposit it in case of necessity or immersion wherein.
Reactor assembly of the present invention can be used for ethylene oxy and changes into oxirane, and comprises reactor tube and be preferably the combination of the shaping carrier material of antigravity system.The unique geometry of this combination provides various beyond thought process advantages.
The antigravity system composition of reactor assembly of the present invention can comprise the shaping carrier material that carries catalyst component.Randomly, the shaping carrier material also carries one or more catalyst promoting agent compositions or catalyst co-promoter composition.Preferred catalyst component is a silver.About the promoter composition, it can comprise, for example, and rare earth metal, magnesium, rhenium and alkali metal such as lithium, sodium, potassium, rubidium and caesium.Wherein, rhenium and alkali metal, particularly, than high basic metal, more preferably as lithium, potassium, rubidium and caesium.Most preferred in than high basic metal is caesium.Can use rhenium promoter and alkali metal-free promoter exists and maybe can use alkali metal promoter and not have the existence of rhenium promoter, or rhenium promoter and alkali metal promoter can be present in the antigravity system all.Except above-mentioned promoter, the rhenium co-accelerator can be present in the antigravity system.This co-accelerator can comprise sulphur, molybdenum, tungsten and chromium.Promoter and co-accelerator compound can be by any proper method as being applied to carrier material by dipping and any form.
The carrier material of shaping carrier material and antigravity system can be any commercially available hear resistance and porous material, is suitable for the carrier material of the promoter composition of making silver catalyst and antigravity system.Carrier material is under the key reaction condition of ethene oxidation and exist under the situation of used chemical compound and should relatively be inertia.Carrier material can comprise that carbon, diamond dust, carborundum, silica, aluminium oxide reach the mixture based on aluminium oxide and silica.Alpha-alumina more preferably because it has big uniform pore size.It is 0.1 to 10 meters squared per gram that carrier material has specific area usually, it preferably is 0.2 to 5 meters squared per gram, more preferably 0.3 to 3 meters squared per gram (is measured by known B.E.T. method, with reference to Brunauer, Emmet and Teller are at the article of J.Am.Chem.Soc.60 (1938) 309-316 page or leaf, and this article combination is as reference of the present invention); Usually being 0.1 to 1.5 cubic centimetre/gram than porosity, preferably is 0.2 to 1.0 cubic centimetre/gram, is most preferably 0.3 to 0.8 cubic centimetre/gram (by the known water determination of adsorption method, its standard is ASTM C20); Common apparent porosity is 20 to 120 volume %, preferably is 40 to 80 volume % (by the known water determination of adsorption method); Usually average pore size is 0.3 to 15 micron, preferably is 1 to 10 micron; And to have diameter usually be that (use Micromeretics Autopore 9200 types are 3.0 * 10 by mercury intrusion to pressure at least 50 weight % for 0.03 to 10 micron hole percentage
8Pa measures (130 ° of contact angles, having surface tension is mercury and the mercury compression correction to applying of 0.473N/m)).
The silver catalyst composition of antigravity system and promoter composition are to deposit or be immersed in the carrier material of antigravity system by any the known standard method of specialty.The concentration range that antigravity system should have silver or silver metal usually is 2 weight % to 30 weight %, or even higher, for example, maximum 40 weight % or more 50 weight %, weight %, weight % is based on the total weight of antigravity system, comprise the weight of carrier material, the weight of catalyst component, that is, silver metal, and the weight of promoter composition.In certain embodiments, the silver-colored composition of antigravity system is 4 weight % to 22 weight % in concentration range preferably, is most preferably 6 to 20 weight %.In other embodiments, preferably being presented on concentration range for the silver-colored composition of antigravity system is 20 to 30 weight %, more preferably is 22 to 28 weight %.This promoter can be 0.003 weight % to 1.0 weight % in concentration range, preferably is 0.005 weight % to 0.5 weight %, is most preferably under 0.01 weight % to the 0.2 weight % to be present in the antigravity system.
Reactor assembly of the present invention is compared with legacy system, when being used for the oxirane manufacture process, with respect to the pressure drop of crossing packed bed, provides the balance of improved pipe packed density (TPD), bed voidage and catalyst hold-up.An importance of the present invention is to recognize that this improvement can for example obtain by the ratio of the nominal outside diameter that changes the hollow cylinder geometry to nominal bore diameter.This is actually beyond thought, makes in the ethylene oxide process for many years and has a lot of effort to attempt the performance of these catalyst of improvement because be used in based on the catalyst of hollow cylinder carrier material.As if yet the performance that trial improves these catalyst by the geometry of revising the hollow cylinder geometry does not also arouse attention.
According to the present invention, compare with the ratio of traditional hollow cylinder carrier material, for example by change, increase the nominal outside diameter of hollow cylinder geometry and the ratio of nominal bore diameter usually and obtain improved balance.As previously mentioned, use the hollow cylinder carrier material can find improved balance to the comparative test of the standard hollow cylindrical support material of the use size that has tradition and use.In this competitive trials, material has same material density usually.Otherwise the difference of proofreading and correct density of material makes the change of managing packed density in fact reflect the change of catalyst hold-up and bed voidage aspect.Pointed out improved balance as the preceding positive result of the test that limits.The example of competitive trials is provided at following example I-IV.
Be equilibrated at various outward appearances or the quality aspect occurs with respect to the pipe packed density (TPD) of the pressure drop of crossing packed bed improved, can understand by the following describes.
Reactor assembly of the present invention comprises having than the shaping carrier material of more bassoon packed density of traditional reactor system or the packed bed of antigravity system.In many cases, because the advantage of gained catalyst performance wishes to increase the pipe packed density.Yet, be generally expected that in order to obtain the upper pipe packed density, when using, the pressure drop meeting of crossing packed bed increases with respect to standard reaction device system.On the other hand, the pressure drop aspect of crossing packed bed that reactor assembly of the present invention unexpectedly is provided in the reactor tube that is contained in reactor assembly is expected low cumulative, in many cases, when comparing with legacy system, minimizing aspect the pressure drop of crossing packed bed, and the correspondence of not having the pipe packed density is lost, and in many cases, has the increase of pipe packed density.
Reactor assembly of the present invention preferably includes has at least pipe packed density big as the traditional reactor system, but the packed bed that preferably surpasses the pipe packed density that legacy system sees, when using, show that pressure drop reduces along with the increase of aforementioned tube packed density.
Relative geometry between caliber and shaping carrier and/or antigravity system is the important feature of reactor assembly of the present invention, and it comprises being filled with and preferably includes the combination of catalyst component with the reactor tube of shaping carrier bed that antigravity system is provided.Also beyond thoughtly be, the carrier bigger with respect to reactor tube can be used as packed bed and is loaded in the reactor tube obtaining managing the increase of packed density, and when reactor assembly uses, and do not seen that big pressure drop crossed packed bed, or see more cumulative than the low pressure drop of expection, particularly based on specific engineering correlation, for example, the Ergun correlation, " transport phenomena " with reference to W.J.Beek and K.M.K.Muttzall work, J.Wiley and Sons Ltd, 1975, p.114.
Be particularly suitable for the packed bed of reactor assembly of the present invention than larger vector and antigravity system, this packed bed has the bigger packed density to the specific dimensions of carrier or antigravity system of expection, but when using, it does not provide the increase of pressure drop gradually, preferably, provide decrescence with respect to the pressure drop that the reactor assembly with same pipe packed density is expected.Attendant advantages is the increase aspect the pipe packed density.
In order to obtain above-mentioned advantage, reactor assembly of the present invention should comprise geometry in particular.Determined that also these geometries are subjected to the influence of reactor caliber, therefore, reactor tube is different to different tube diameters with the relative geometry of shaping carrier usually.For having internal diameter for less than 28 millimeters reactor tube, the ratio ranges of reactor tube internal diameter and carrier system external diameter should be 1.5 to 7, preferably is 2 to 6, is most preferably 2.5 to 5.Surpass 28 millimeters reactor tube for having internal diameter, the ratio ranges of reactor tube internal diameter and carrier system external diameter should be 2 to 10, is 2.5 to 7.5 preferably, is most preferably 3 to 5.
The ratio of the external diameter of the carrier of antigravity system and aperture or internal diameter is another key property of reactor assembly of the present invention.For having internal diameter for less than 28 millimeters reactor tube, the ratio ranges of the external diameter of the carrier of antigravity system and aperture or internal diameter can be 2.3 to 1000, preferably is 2.6 to 500, is most preferably 2.9 to 200.Surpass 28 millimeters reactor tube for having internal diameter, the ratio ranges of the external diameter of the carrier of antigravity system and aperture or internal diameter can be 2.7 to 1000, is 3 to 500 preferably, is most preferably 3.3 to 250.
Though the aperture of shaping carrier material is relatively little very important, it is also very important that the endoporus of carrier has at least some sizes.Found that the void space that is limited by the aperture is providing certain advantage aspect manufacturing catalyst and the catalysis characteristics thereof.Though do not wish to be defined in any particular theory, it is believed that void space that the aperture by hollow cylinder provides is for example allowed to improve the deposition of catalyst component on carrier, and improve further operation by dipping, for example dry.The advantage of using relative smaller aperture due also is that the shaping carrier material has higher crushing strength with respect to the carrier material with larger aperture.Preferably make at least one end in hole, normally the internal diameter diameter at two ends is at least 0.1 millimeter, more preferably is at least 0.2 millimeter.Internal diameter preferably is at least 5 millimeters, preferably is maximum 2 millimeters, for example, and 1 millimeter or 1.5 millimeters.
Another key property of reactor assembly of the present invention is that the carrier of the packed bed antigravity system of reactor assembly of the present invention has length and external diameter natural scale scope is 0.5 to 2.0, preferably is 0.8 to 1.5, is most preferably 0.9 to 1.1.
The general introduction of the desired scope of the physical dimension of reactor assembly of the present invention is presented at table 1 and 2.Table 1 demonstration has the relative geometry less than the shaping carrier of the reactor tube of 28 mm dias.Table 2 shows the relative geometry of the shaping carrier of the reactor tube with at least 28 mm dias.Less reactor tube can have the caliber scope little to 21 millimeters or even littler, for example, 20 millimeters.Therefore, the caliber scope of the less reactor tube of reactor assembly of the present invention can be 20 millimeters or 21 millimeters to being lower than 28 millimeters.It is high to 60 millimeters or even bigger that big reactor tube can have the caliber scope.Therefore, the caliber scope of the big reactor tube of reactor assembly of the present invention can be 28 millimeters to 60 millimeters.
About the caliber scope is 28 millimeters to 60 millimeters, and particularly when caliber was 39 millimeters, the nominal outside diameter of carrier and the ratio of nominal bore diameter preferably were:
When the external diameter scope is 10.4 millimeters to 11.6 millimeters, be at least 4.5; Or
When the external diameter scope is 9.4 millimeters to 10.6 millimeters, greater than 3.4, particularly at least 3.6; Or
When the external diameter scope is 8.4 millimeters to 9.6 millimeters, be at least 2.6, especially in 2.6 to 7.3 scope.
Table 1: have of the present invention reactor assembly geometry of caliber less than 28 millimeters reactor tube
Caliber/antigravity system external diameter | Antigravity system length/antigravity system external diameter | Catalyst external diameter/internal diameter | |
Wide | 1.5-7 | 0.5-2 | 2.3-1000 |
In | 2-6 | 0.8-1.5 | 2.6-500 |
Narrow | 2.5-5 | 0.9-1.1 | 2.9-200 |
Table 2: have of the present invention reactor assembly geometry of caliber at least 28 millimeters reactor tube
Caliber/antigravity system external diameter | Antigravity system length/antigravity system external diameter | Catalyst external diameter/internal diameter | |
Wide | 2-10 | 0.5-2 | 2.7-1000 |
In | 2.5-7.5 | 0.8-1.5 | 3.0-500 |
Narrow | 3-5 | 0.9-1.1 | 3.3-250 |
The reactor pipe range can be in the reaction zone that can be provided at effectively between feed reactants and antigravity system suitably time of contact to obtain requiring any length of product.Usually, as mentioned above, the reactor pipe range surpasses 3 meters, and its scope preferably is 3 meters to 15 meters.Any length part that the total length of reactor tube can be filled with antigravity system or reactor tube can be filled with antigravity system so that the packed bed of the antigravity system with degree of depth to be provided.Therefore, the bed degree of depth can surpass 3 meters, and its scope preferably is 3 meters to 15 meters.
In common practice of the present invention, the major part of reactor assembly packed bed of the present invention comprises the shaping carrier material with geometry described herein.Therefore, usually, the packed bed major part of reactor assembly, promptly, at least 50%, comprise antigravity system, particularly with the geometry that clearly limits, at least 80% of catalyst filling, but preferably be at least 85%, be most preferably at least 90% and comprise the antigravity system that clearly limits.When relating to the percentage of the packed bed that comprises antigravity system, the whole numbers that mean each antigravity system particle with specific dimensions described herein multiply by 100 to the ratio of whole numbers of being contained in the antigravity system particle in the packed bed.In another embodiment, when relating to the percentage of the packed bed that comprises antigravity system, the bulk volume that means the antigravity system particle with specific dimensions described herein multiply by 100 to the ratio of the bulk volume that is contained in all the antigravity system particles in the packed bed.In another embodiment, when relating to the percentage of the packed bed that comprises antigravity system, the weight that means the antigravity system particle with specific dimensions described herein multiply by 100 to the ratio of the weight that is contained in all the antigravity system particles in the packed bed.
The pipe packed density of the antigravity system bed of reactor assembly of the present invention can be key property of the present invention; Because the increase of the pipe packed density that the improvement of catalyst performance can obtain from the unique geometry of use reactor assembly of the present invention.Usually, the pipe packed density of catalyst filling system bed depends on that the reactor tube internal diameter reaches in order to form the specific support properties of materials such as the density of shaping carrier.
For less reactor tube internal diameter, the pipe packed density of packed bed can be lower than the pipe packed density of the packed bed of big reactor tube internal diameter usually.Therefore, for example, when carrier material was mainly Alpha-alumina, the pipe packed density that has inboard reactor caliber and be a reactor assembly packed bed of the present invention of 21 millimeters can be low to moderate but above 550 kilograms/cubic metre.Have reactor tube for the reactor tube with big inside tube footpath and those, wish to have accessible and still can realize the big pipe packed density of advantage of the present invention than minor diameter.When carrier material was mainly Alpha-alumina, this pipe packed density can surpass 650 kilograms/cubic metre or can be greater than 700 kilograms/cubic metre, even greater than 850 kilograms/cubic metre.The pipe packed density is preferably greater than 900 kilograms/cubic metre, and the pipe packed density is most preferably above 920 kilograms/cubic metre.The pipe packed density is usually less than 1200 kilograms/cubic metre, more specifically, is lower than 1150 kilograms/cubic metre.
Referring now to Fig. 1, its explanation comprises elongated tubular 12 and the reactor assembly of the present invention 10 that is contained in the packed bed 14 in the elongated tubular 12.Elongated tubular 12 has the inboard caliber 20 and the reaction zone diameter 20 in tube wall 16 and inside tube surface 18 and defined reaction district, includes packed bed 14 in the reaction zone.Elongated tubular 12 has pipe range 22 and the packed bed 14 that is contained in the reaction zone has a degree of depth 24.In the bed degree of depth 24 outsides, elongated tubular 12 can comprise the separation bed of the particle of non-catalytic material, for example is used for and the heat exchange of charging and/or the other this bed that separates, and for example is used for the heat exchange with product.Elongated tubular 12 further has inlet pipe end 26, and the charging that comprises ethene and oxygen can import wherein, and outlet pipe end 28, and the product that comprises oxirane and ethene can reclaim from it.It should be noted that if any the ethene of the ethene in, the product for the charging by unconverted reactor zone.The typical conversions of ethene surpasses 10 moles of %, but in some cases, conversion ratio can be lower.
The packed bed 14 that is included in the reaction zone is made up of the bed of antigravity system on the carrier 30, as described in Figure 2.According to the present invention, antigravity system 30 has the general hollow cylinder geometry of nominal length 32, nominal outside diameter 34 and nominal inboard or internal diameter diameter 36 on the carrier.
Those skilled in the art understands that term " cylinder " needn't mean the hollow cylinder geometry and only comprise correct cylinder.Term " cylinder " means and comprises with correct the small of cylinder and departing from.For example, the cross section perpendicular to the hollow cylinder geometry neighboring of cylinder axis needn't be correct circular 71 (as shown in Figure 7).In addition, the axis of the hollow cylinder geometry external diameter that can be approximate straight line and/or hollow cylinder geometry can be approximate constant along axis.Small departing from comprises, for example, the outer periphery of cylinder can be positioned to have virtually by two and be the situation in imaginary tubular space same diameter, that imaginary correct coaxial cylinders limits, thereby the diameter of imaginary inner cylinder be imaginary outer cylinder diameter at least 70%, more typically be at least 80%, particularly at least 90%, select imaginary cylinder, the ratio that makes its diameter is for as far as possible near 1.In this case, the diameter of imaginary outer cylinder is considered as the external diameter of hollow cylinder geometry.Fig. 7 illustrates outer periphery 72, imaginary outer cylinder 73 and the imaginary inner cylinder 74 of hollow cylinder geometry with the sectional view of obtaining perpendicular to the axis of imaginary cylinder 73 and 74.
Equally, those skilled in the art can understand that the hole of hollow cylinder geometry needn't be for correctly cylindric, and the axis in hole can be approximate straight line, and the aperture can be approximate constant, and/or the axis in hole can be offset, or can meet at right angles with respect to the axis of cylinder.If when the aperture changed on the length of internal diameter, the aperture was considered as the maximum gauge at nose end.If the cross section in hole is not for correct when circular, the wideest size is considered as the aperture.In addition, the void space that is provided by the hole can be divided into two or more holes, for example, is divided into 2,3,4 or 5 holes, and in this case, the aperture makes the total sectional area in hole equal to have the sectional area in the single hole of the diameter that this paper defines.
In a preferred embodiment, the hollow cylinder geometry wishes to become the cylinder that has along the hole of cylinder axis.
Notice, the hollow cylinder geometry is of a size of nominal and is similar to, needn't be accurate because make the method for the caking that is shaped.
Provide unique geometrical combination of the physical dimension of antigravity system 30 on the beyond thought inboard caliber that reduces of pressure drop or reaction zone diameter 20 and the carrier, when using and during with respect to legacy system, not having the remarkable minimizing of pipe packed density aspect.In many cases and preferably, the pipe packed density of reaction system of the present invention is greater than the pipe packed density of traditional reaction system, and the minimizing of pressure drop still is provided in use.
The essence physical dimension of antigravity system 30 is the ratio of 32 pairs of nominal outside diameters 34 of nominal length.This size as above describes in detail.
The ratio that another essence physical dimension of antigravity system 30 is 34 pairs of nominal outside diameters 36 of nominal outside diameter.This size as above describes in detail.
The relative size that antigravity system 30 and elongated tubular are 12 is importance of the present invention; Because the Pressure Drop Characteristics that these size decision pipe packed densities and reactor assembly 10 are correlated with.These sizes as above describe in detail.
The another way that defines antigravity system is with reference to its nominal dimension.About the 8 millimeters catalyst of standard with hollow cylinder geometry, the external diameter of cylinder is generally 8 millimeters but can be 7.4 millimeters to 8.6 millimeters.The length of cylinder is generally 8 millimeters but can be 7.4 millimeters to 8.6 millimeters.For use of the present invention, internal diameter can be at least 0.1 millimeter or 0.2 millimeter, preferably is 0.5 millimeter to 3.5 millimeters, more preferably be 0.5 millimeter to below 3 millimeters.
For 9 millimeters catalyst of the standard with hollow cylinder geometry, the external diameter of cylinder is generally 9 millimeters but can be 8.4 millimeters to 9.6 millimeters.The length of cylinder is generally 9 millimeters but can be 8.4 millimeters to 9.6 millimeters.For use of the present invention, the internal diameter of 9 millimeters catalyst of standard can be at least 0.1 millimeter or 0.2 millimeter, preferably is 0.5 millimeter to 3.5 millimeters, more preferably is 1.25 millimeters to 3.5 millimeters.
For 10 millimeters catalyst of the standard with hollow cylinder geometry, the external diameter of cylinder is generally 10 millimeters but can be 9.4 millimeters to 10.6 millimeters.The length of cylinder is generally 10 millimeters but can be 9.4 millimeters to 10.6 millimeters.For use of the present invention, the internal diameter of 10 millimeters catalyst of standard can be at least 0.1 millimeter or 0.2 millimeter, is preferably 0.5 millimeter to 4.0 millimeters, more preferably is 0.5 millimeter to 3 millimeters, even more preferably is 0.5 millimeter to 2.8 millimeters.
For 11 millimeters catalyst of the standard with hollow cylinder geometry, the external diameter of cylinder is generally 11 millimeters but can be 10.4 millimeters to 11.6 millimeters.The length of cylinder is generally 11 millimeters but can be 10.4 millimeters to 11.6 millimeters.For use of the present invention, the internal diameter of 11 millimeters catalyst of standard can be at least 0.1 millimeter or 0.2 millimeter, preferably is 0.5 millimeter to 3.5 millimeters, more preferably is 0.5 millimeter to 2.5 millimeters.
Many variations of antigravity system size are because the mode of manufacturing hollow cylinder carrier material causes.This manufacture method is known and comprise that standard method is as extruding and ball wafer production method in the catalyst carrier manufacturing technology.
Fig. 3 is a schematic diagram, and total manufacture method that oxirane is shown 40 is used shell-pipe in pipe 42, and it is provided with a plurality of reactor assemblies, as shown in Figure 1.Usually, the reactor assembly of Fig. 1 and a plurality of other reactor assemblies are combined into to restrain and are used to insert in the shell of shell-pipe in pipe.
The charging that comprises ethene and oxygen is through pack into the pipe side of shell-pipe in pipe 42 of conduit 44, wherein this charging be contained in interior antigravity system and contact.Utilization of Heat of Reaction is removed as oil, coal or water by pack into the heat-transfer fluid of shell side of shell-pipe in pipe 42 of conduit 46, and heat-transfer fluid removes by the shell of conduit 48 from shell-pipe in pipe 42.
Comprise oxirane, unreacting ethylene, unreacted oxygen and randomly, the product of other product such as carbon dioxide and water reclaims and leads to piece-rate system 52 by conduit 50 from the reactor assembly pipe of shell-pipe in pipe 42.Piece-rate system 52 provides separating of oxirane and ethene, if when having carbon dioxide, also provides separating of carbon dioxide and water.Extraction fluid such as water can be used to separate these compositions and utilize conduit 54 to import in the piece-rate system 52.If the quintessence that contains oxirane is got fluid self-separation system 52 by conduit 56, and when existing, unreacting ethylene and carbon dioxide from piece-rate system 52 by conduit 58.The carbon dioxide that separates passes through conduit 61 from piece-rate system 52.A part of air-flow by conduit 58 can be used as purge flow and removes by conduit 60.All the other air communication are crossed conduit 62 to recirculation compressor reducer 64.Mix flow passes through to recirculation compressor reducer 64 by conduit 66 and with the ethene combination of recirculation by conduit 62 in the incoming flow that contains ethene and oxygen.Recirculation compressor reducer 64 enters air-flow in the conduit 44, thereby this discharge currents is packed in the inlet of shell-pipe in pipe 42 pipe sides.Piece-rate system 52 preferably with carbon dioxide lower by the amount in the incoming flow of conduit 44, for example,,, or operate in the mode of the scope of 0.5 to 1 mole of % preferably at 1 mole below the % at 2 moles below the %.
The oxirane that epoxidation process produces can change into ethylene glycol, glycol ether or alkanolamine.
Changing into ethylene glycol or glycol ether can comprise, for example, suitably uses acid or base catalyst to make oxirane and water reaction.For example, be used for making and be mainly ethylene glycol and be glycol ether on a small quantity, oxirane can acidic catalyst as sulfuric acid based on complete reaction mixture 0.5-1.0 weight % in the presence of, at 50-70 ℃, under the 100kPa absolute value, in liquid phase reactor, or at 130-240 ℃, under the 2000-4000kPa absolute value, preferably catalyst not in the presence of in gas-phase reaction with the reaction of the water of 10 times of molar excess.When if the ratio of water is hanged down, the ratio regular meeting of glycol ether in reactant mixture increases.The glycol ether of so making can be diether, three ethers, tetraether or ether subsequently.Other glycol ether can be by transforming oxirane and alcohol, and particularly first alcohol prepares by alcohol displacement at least a portion water as methyl alcohol or ethanol.
Changing into alkanolamine can comprise oxirane and amine such as ammonia, alkylamine or dialkylamine reaction.Can use anhydrous or water-based ammonia.Anhydrous ammonia is generally used for the manufacturing of strand alkanolamine.Change into the method for alkanolamine for can be applicable to oxirane, can reference, for example, and US-A-4845296, this document is in conjunction with as reference of the present invention.
Ethylene glycol and glycol ether can be used for various commercial Application, for example, and fields such as food, beverage, tobacco, cosmetics, thermoplastic polymer, curable resin system, detergent, heat transfer system.Alkanolamine can be used for, for example, and the processing of natural gas (" desulfurization ").
Following example plans to be used for illustrating advantage of the present invention rather than to be used for undeservedly limiting the scope of the invention.
Example I
This example I presents in order to assessment with respect to the pressure drop of the reactor assembly of the present invention of standard reaction device system and the test procedure of pipe packed density feature.
Various hollow cylinder carriers with different size and geometry are tested in having the commercial length reactor tube of 39 millimeters internal diameters or 21 millimeters internal diameters.Set up reactor tube to cross the difference pressure drop of carrier bed with mensuration.Measure the pipe packed density of carrier bed.
The specific support use standard funnel stowage of testing is packed in the reactor tube.The carrier weighing is measured its quality before in the reactor tube of packing into.After reactor tube was packed carrier into, 0.79MPa (100psig) air source was used for carrying out blowing in 15 seconds dust downwards.Measure the carrier bed height.
The pipe packed density is measured by pack into the height of mensuration of carrier quality in the reactor tube, carrier bed and the internal diameter of reactor tube of use.The pipe packed density has every volume mass unit and is defined by following formula:
4m/πd
2h
Wherein: m is the interior carrier quality of reactor tube of packing into,
D is the diameter of reactor tube, and
H is the height that is contained in the carrier bed in the reactor tube.
After reactor tube is packed carrier into, its sealing is tested under 1.342MPa (180psig) pressure.Reactor tube is provided with inlet and outlet.Nitrogen pressure imports in the inlet of filling reactor pipe down about 1.136MPa (150psig).(the Reynolds numbers of particles surpasses 700 for each flow velocitys of about 11 kinds of different nitrogen flow rates in the turbulence state, with reference to W.J.Beek and K.M.K.Muttzall, " transport phenomena ", J.Wiley and Sons Ltd, 1975, p.114), determine to cross the difference pressure drop (pressure drop) of the carrier bed of reactor tube by measuring tube inlet pressure and pipe outlet pressure.Also measure the inlet and the outlet temperature of nitrogen.Length assessment pressure drop with every unit packed bed.The difference of the catalyst hold-up that causes for the difference that reflects by the carrier geometry is to the little difference correction pipe packed density of the characteristic density of material of different carriers.
Example II
Example II illustrate to have nominal length to diameter (L/D) than the general introduction that is the result of the described test procedure of hollow cylinder carrier use-case I 0.5 or 1.0, that be packed into 5 millimeters, 6 millimeters, 7 millimeters, 8 millimeters of nominal dimensions in 39 millimeters reactor tubes and 9 millimeters.Classify the details of carrier dimensions down as:
9 millimeters: L/D=1.0,3.85 millimeters in aperture
9 millimeters: L/D=0.5,3.90 millimeters in aperture
8 millimeters: L/D=1.0,3.20 millimeters in aperture (" 8 millimeters of standards ")
8 millimeters: L/D=0.5,3.30 millimeters in aperture
7 millimeters: L/D=1.0,2.74 millimeters in aperture
7 millimeters: L/D=1.0,2.75 millimeters in aperture
6 millimeters: L/D=1.0,2.60 millimeters in aperture (" 6 millimeters of standards ")
6 millimeters: L/D=1.0,2.60 millimeters in aperture
5 millimeters: L/D=1.0,2.40 millimeters in aperture
5 millimeters: L/D=1.0,2.70 millimeters in aperture
The % of the pressure drop of crossing carrier bed is changed the summary data that changes with % with respect to the pipe packed density of 8 millimeters carriers of standard be shown in Fig. 4.As shown in the figure, for less than 8 millimeters carrier dimensions and have L/D than all carrier dimensions that are 0.5, the pressure drop meeting of crossing carrier bed increases.Yet Fig. 4 data presented is presented in 39 millimeters reactor tubes, has L/D than the improved pressure drop that provides for bigger 9 millimeters carriers of 1.0 with respect to 8 millimeters carriers of standard.
Example III
Example III shows and to enter in 39 millimeters reactor tubes the result of the described test procedure of use-case I to having 9 millimeters of nominal dimensions, 10 millimeters and 11 millimeters than the cylindrical support that is 1.0 with nominal L/D.A plurality of carriers are the filled circles cylindrical shell, and other carriers are the hollow cylinder with different inner diameters, as shown in Figure 5.The % of the pressure drop of crossing carrier bed is changed the summary data that changes with % with respect to the pipe packed density of 8 millimeters carriers of standard be shown in Fig. 5.
The data that Fig. 5 presents show the beyond thought reduction of the unique combination result's who uses reactor tube and carrier geometry pressure drop.About having the aperture to the ratio of external diameter 9 millimeters carriers greater than 0.138 (external diameter is lower than 7.2 to the ratio in aperture), improvement with respect to the pressure drop of 8 millimeters carriers of standard of testing is arranged, 10 millimeters and 11 millimeters carrier geometries to all tests then have the improvement with respect to the pressure drop of 8 millimeters carriers of standard.
About the pipe packed density, can see improvement in 9 millimeters support tube packed densities with respect to 8 millimeters carriers of standard, the ratio of external diameter is equal to or less than the geometry of about 0.38 (external diameter is to the ratio at least 2.6 in aperture) for aperture wherein, and 10 millimeters carriers, can see improvement to having the aperture to the geometry that the ratio of external diameter is equal to or less than about 0.28 (external diameter greater than 3.4, is preferably at least 3.6 to the ratio in aperture).About 11 millimeters carriers, to external diameter internally the footpath ratio greater than the pressure drop of the geometry of all tests of 4.5 with manage aspect the packed density, all can see improvement.
Example IV
Example IV shows that it is 0.5 or 1.0 to fill and enter in 21 millimeters reactor tubes the result of the described test procedure of use-case I that 5 millimeters of nominal carrier dimensions, 6 millimeters, 7 millimeters, 8 millimeters and 9 millimeters are had nominal L/D ratio.The details of carrier dimensions is described in example II.
The % of the pressure drop of crossing carrier bed is changed the summary data that changes with % with respect to the pipe packed density of 6 millimeters carriers of standard be shown in Fig. 6.As shown in the figure, to 8 millimeters with 9 millimeters carrier dimensions, can see the improvement of pressure drop and be 7 millimeters carriers of 1.0 having L/D, can see the improvement of pressure drop.Along with selected carrier, can reach the improvement of pressure drop.And can't reduce the pipe packed density, particularly when increasing external diameter to the ratio of internal diameter.
Example V (hypothesis)
Described each carrier of example II-IV is the silver catalyst that comprises carrier with the solution impregnation that comprises silver with formation.Then, comprising ethene contacts with catalyst to form oxirane under proper condition with the incoming flow of oxygen.
Example VI
Example VI presents and relevant is used to prepare as the characteristic of two kinds of carriers (that is, support C and carrier D) of catalyst as described in the example VII and the information (with reference to table 3) of geometry.
Table 3: the characteristic of carrier
Characteristic | Support C | Carrier D |
The characteristic water absorption rate, % body packed density, kilogram/cubic meter (pound/stere) ASTM consumption rate, the average dull and stereotyped crushing strength of %, N (1bf) surface area, m 2/g | 46.5 843(52.7) 14.7 130(29.3) 0.77 | 50.4 788(49.2) 16.5 180(40.4) 0.78 |
The geometry nominal dimension, the millimeter average length, mm length, scope, mm dia, the millimeter aperture, millimeter ratio length/external diameter | 8 7.7 6.6-8.6 8.6 1.02 0.90 | 8 7.7 6.6-8.6 8.6 1.02 0.90 |
Example VII
This example VII explanation can be used for Preparation of catalysts of the present invention.
Catalyst C:
The catalyst C that use prepares by volume C dipping from the known method of US-A-4766105, this United States Patent (USP) combination is as reference of the present invention.Last catalyst C composition is 17.8%Ag, 460ppm Cs/g catalyst, 1.5 micromole Re/ gram catalyst, 0.75 micromole W/ gram catalyst and 15 micromole Li/ gram catalyst.
Catalyst D:
Prepare catalyst D with two impregnation steps.In first impregnation steps, except adulterant does not join silver-colored solution,, use silver-colored solution impregnating carrier according to the program of catalyst C.After drying, the dry catalyst precursor of crossing of gained contains 17 weight % silver approximately.Then, the dry catalyst precursor of crossing is with containing the solution impregnation of silver with adulterant.Last catalyst D composition is 27.3%Ag, 550ppm Gs/g catalyst, 2.4 micromole Re/ gram catalyst, 0.60 micromole W/ gram catalyst and 12 micromole Li/ gram catalyst.
Catalyst E:
Replace second dipping solution except tungsten compound is present in first dipping solution, the program according to catalyst D is implemented prepares catalyst E with two impregnation steps.Last catalyst E composition is 27.3%Ag, 560ppm Cs/g catalyst, 2.4 micromole Re/ gram catalyst, 0.60 micromole W/ gram catalyst and 12 micromole Li/ gram catalyst.
Though the present invention is illustrated according to preferred embodiment, those skilled in the art can be done rationally to change and remodeling to it.This changes and remodeling should be in the scope of described scope of the present invention and appending claims.
Claims (20)
1. reactor assembly comprises:
Have the pipe range in defined reaction district and the elongated tubular of caliber; The packed bed of carrier material of wherein being shaped is included in this reaction zone; And the carrier material that wherein is shaped has the hollow cylinder geometry that is limited by nominal length, nominal outside diameter and nominal bore diameter, makes that nominal length is 0.5 to 2 to the ratio ranges of nominal outside diameter, and makes
When caliber during less than 28 millimeters, the ratio of nominal outside diameter and nominal bore diameter surpasses 2.3, and the ratio ranges of caliber and external diameter is 1.5 to 7, reaches
When caliber was at least 28 millimeters, the ratio of nominal outside diameter and nominal bore diameter surpassed 2.7, and the ratio ranges of caliber and external diameter is 2 to 10.
2. reactor assembly comprises:
Have the pipe range in defined reaction district and the elongated tubular of caliber; The packed bed of carrier material of wherein being shaped is included in the reaction zone; And the carrier material that wherein is shaped has the hollow cylinder geometry that is limited by nominal length, nominal outside diameter and nominal bore diameter, makes
The ratio ranges of nominal length and nominal outside diameter is 0.5 to 2, and
The ratio of nominal outside diameter and nominal bore diameter provides positive result of the test, and makes
When caliber during less than 28 millimeters, the ratio ranges of caliber and nominal outside diameter is 1.5 to 7, and when caliber was at least 28 millimeters, this ratio ranges was 2 to 10;
Wherein " positive result of the test " is defined as the quotient reduction of numerical value and the numerical value of packed density of the length pressure drop of every unit packed bed, these numerical value obtain in pressure is turbulent flow under the 1.136Mpa (150psig), at nitrogen by the test packed bed, relative comparison quotient obtains in an identical manner, except the hollow cylinder geometry of same vehicle material is to be limited by following, promptly
When caliber during less than 28 millimeters, being defined as nominal outside diameter and being 6 millimeters and nominal bore diameter is 2.6 millimeters, and when caliber is at least 28 millimeters, and being defined as nominal outside diameter and being 8 millimeters and nominal bore diameter is 3.2 millimeters, and
The ratio of nominal length and nominal outside diameter is defined as 1.
3. reactor assembly as claimed in claim 2 is characterized in that defining this hollow cylinder geometry, makes,
When caliber is during less than 28 millimeters, nominal outside diameter surpasses 2.3 to the ratio of nominal bore diameter, and
When caliber during at least 28 millimeters, nominal outside diameter surpasses 2.7 to the ratio of nominal bore diameter.
4. as each reactor assembly among the claim 1-3, it is characterized in that
The caliber scope is 28 millimeters to 60 millimeters, and
Nominal outside diameter to the ratio of nominal bore diameter is
When the external diameter scope is 10.4 millimeters to 11.6 millimeters, be at least 4.5; Or
When the external diameter scope is 9.4 millimeters to 10.6 millimeters, greater than 3.4; Or
When the external diameter scope is 8.4 millimeters to 9.6 millimeters, be at least 2.6.
5. reactor assembly as claimed in claim 4 is characterized in that this nominal outside diameter to the ratio of nominal bore diameter is
When the external diameter scope is 10.4 millimeters to 11.6 millimeters, be at least 4.5;
When the external diameter scope is 9.4 millimeters to 10.6 millimeters, be at least 3.6; Or
When the external diameter scope was 8.4 millimeters to 9.6 millimeters, scope was 2.6 to 7.3.
6. as each reactor assembly among the claim 1-5, it is characterized in that this caliber is about 39 millimeters.
7. as each reactor assembly among the claim 1-6, it is characterized in that the internal diameter of this hollow cylinder geometry is at least 0.5 millimeter.
8. as each reactor assembly among the claim 1-7, it is characterized in that when caliber when being lower than 28 millimeters, the ratio ranges of nominal outside diameter and nominal bore diameter is 2.6 to 500, and when caliber during at least 28 millimeters, its scope is 3.0 to 500.
9. reactor assembly as claimed in claim 8, it is characterized in that when caliber when being lower than 28 millimeters, the ratio ranges of nominal outside diameter and nominal bore diameter is 2.9 to 200, and when caliber during at least 28 millimeters, its scope is 3.3 to 250.
10. as each reactor assembly among the claim 1-9, it is characterized in that this pipe range scope is 3 to 15 meters.
11., it is characterized in that 50% packed bed comprises the shaping carrier material as each reactor assembly among the claim 1-10.
12. as each reactor assembly among the claim 1-11, it is characterized in that when caliber when being lower than 28 millimeters, the ratio ranges of caliber and nominal outside diameter is 2 to 6, and when caliber during at least 28 millimeters, its scope is 2.5 to 7.5.
13. as the reactor assembly of claim 12, it is characterized in that when caliber when being lower than 28 millimeters, the ratio ranges of caliber and nominal outside diameter is 2.5 to 5, and when caliber during at least 28 millimeters, its scope is 3 to 7.
14. as each reactor assembly among the claim 1-13, it is characterized in that this shaping carrier material mainly comprises Alpha-alumina, and packed bed has every cubic metre greater than 550 kilograms pipe packed density.
15., it is characterized in that this shaping carrier material carrying catalyst component as each reactor assembly among the claim 1-14.
16., it is characterized in that this catalyst component comprises silver as the reactor assembly of claim 15.
17. a method of making oxirane, this method comprises:
Reactor assembly as claim 15 or 16 is provided, and wherein elongated tubular has inlet pipe end and outlet pipe end;
The charging that will comprise ethene and oxygen imports in the inlet pipe end; And
If any, export pipe end certainly and reclaim the product that comprises oxirane and unconverted ethene.
18. as the method for claim 17, it is characterized in that this reaction zone remains under the suitable ethylene oxidation reactions condition, comprise that temperature range is that 150 ℃ to 400 ℃ and pressure limit are 0.15Mpa to 3Mpa.
19. one kind is used oxirane for making ethylene glycol, glycol ether or 1, the method of 2-alkanolamine, comprise that transforming oxirane becomes ethylene glycol, glycol ether or 1, the 2-alkanolamine, wherein oxirane is by being obtained by the method for preparing oxirane as claim 17 or 18.
20. a catalyst, wherein catalyst comprises the silver by the carrying of shaping carrier material, and the shaping carrier material has the hollow cylinder geometry that is defined by nominal length, nominal outside diameter and nominal bore diameter, makes
The ratio ranges of nominal length and nominal outside diameter is 0.5 to 2,
The ratio of nominal outside diameter and nominal bore diameter surpasses 2.7, and the ratio ranges of caliber and external diameter is 2 to 10.
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US10/431,035 US20040225138A1 (en) | 2003-05-07 | 2003-05-07 | Reactor system and process for the manufacture of ethylene oxide |
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US10/815,276 US8043575B2 (en) | 2003-05-07 | 2004-04-01 | Reactor system and process for the manufacture of ethylene oxide |
US10/815,276 | 2004-04-01 | ||
PCT/US2004/014087 WO2004101141A1 (en) | 2003-05-07 | 2004-05-05 | A reactor system and process for the manufacture of ethylene oxide |
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2004
- 2004-04-01 US US10/815,276 patent/US8043575B2/en active Active
- 2004-05-05 CN CN2004800122319A patent/CN1784267B/en not_active Expired - Lifetime
- 2004-05-05 TW TW093112590A patent/TW200505883A/en unknown
-
2005
- 2005-10-21 ZA ZA200508559A patent/ZA200508559B/en unknown
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CN102093312A (en) * | 2010-12-20 | 2011-06-15 | 浙江大学 | Epoxyethane synthesis method and production device thereof |
CN102093312B (en) * | 2010-12-20 | 2013-01-02 | 浙江大学 | Epoxyethane synthesis method and production device thereof |
Also Published As
Publication number | Publication date |
---|---|
CN1784267B (en) | 2010-09-08 |
US20040225138A1 (en) | 2004-11-11 |
US8043575B2 (en) | 2011-10-25 |
ZA200508559B (en) | 2007-04-25 |
US20050019235A1 (en) | 2005-01-27 |
TW200505883A (en) | 2005-02-16 |
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